1. Field of the Invention
The present invention relates to separators for use in silver-zinc batteries, and more particularly to separators made of micro-porous membranes.
2. Description Relative to the Prior Art
Silver zinc batteries have the highest power among the alkaline batteries. They are composed of at least one pair of electrodes of opposite polarity, usually a series of adjacent electrodes of alternating polarity, positive silver electrode and a negative zinc electrode, and KOH as electrolyte. Separators are positioned in the cell between the adjacent electrodes to prevent shorting between electrodes from metal migration. The inclusion of these separators is well known in battery technology, and has been the subject of a number of patents. The separators are porous, allowing the migration of electrolyte through the separator, but preventing migration of metal particles.
Silver zinc batteries have an energy density per volume 2.5 times greeter than those of lead acid batteries and 1.8 times higher than those of nickel cadmium. The energy density per weight of a silver zinc battery is 3.7 times higher than a lead acid battery and 2.0 times higher than a nickel cadmium battery. In addition there are less environmental concerns with silver zinc batteries than with lead acid or nickel cadmium and silver-zinc batteries are safer than lithium batteries.
However, silver zinc batteries have significantly shorter cycle life than the other batteries. They have a high capacity loss and short cycle life and higher labor assembly costs than other batteries. As a result, silver zinc batteries have, up to now, been limited in their applications to those areas where high power is required, such as the military.
Cellophane is the primary choice for separators in the vast majority of both military and commercial secondary silver zinc batteries. It has been found, however, that the Cellophane separator is the primary cause of the short comings of silver zinc batteries. This Cellophane separator has been the major obstacle for producing an enhanced silver zinc battery with cycle life, calendar life and performance comparable to alkaline batteries.
In prior art silver zinc cells, either the positive or the negative electrode is commonly wrapped with 5 to 8 layers of Cellophane. An electrolyte absorbing layer is usually positioned between the separator and the electrode. Pellon (nylon) or a surface treated non-woven polyolefine mat is usually used as absorbing layer in silver battery systems.
In prior art the Cellophane acts as a xe2x80x9csacrificingxe2x80x9d layer between the electrodes of silver zinc batteries. In effect, the Cellophane layer is progressively consumed as it performs its function. Cellophane is not stable in KOH or silver oxide, a powerful oxidizing agent present in silver battery systems, which attacks and oxidizes the Cellophane. Water also attacks Cellophane and makes it swell. In order to reduce the Cellophane degradation in a KOH solution a higher concentration must be used, 45% KOH is common. In a low KOH concentration (i.e., high water content) Cellophane swells and degrades rapidly. At room temperature, the electrical resistance of a 45% KOH solution is significantly higher than a 31% KOH solution. The performance of a battery with 45% KOH is, therefore, poorer than a battery that uses 31 % KOH solution as electrolyte, assuming all other parameters stay the same.
Thus, the cycle life and calendar life of today""s silver zinc battery is very short due to usage of Cellophane as the main separator. The cycle life of a silver zinc battery is primarily limited to the number of sacrificing Cellophane layers used in a given cell. However, this number is limited to eight layers because Cellophane does not increase cycle life if more than eight layers are added. Eight layers of Cellophane can only withstand a maximum wet life of 2-3 years in a 45% KOH solution and designing a cell with more Cellophane layers will not increase the calendar life and it will only reduce the energy density. The calendar life of a cell using Cellophane is even shorter in a 31% KOH solution.
Celgard(copyright)1 is used as an alternative to Cellophane as a separator for some alkaline battery applications. Celgard is a polyolefine membrane produced by sheet extrusion and gradual stretching of the sheet to produce a porous membrane. The pore diameters of Celgard are large, 1000-2000 angstrom range, (U.S. Pat. Nos. # 3,558,764 and # 5,667,911 ) and not uniform, the pore diameters in machine direction are significantly larger than cross machine direction. Although the application of Celgard is described in the prior art, Celgard is not suitable for silver zinc battery application due to its large pore size and low pore tortuosity. The cycle life of a silver zinc battery with Celgard separator is significantly shorter than the one with Cellophane. This is due to a larger pore diameter and faster rate of colloidal silver migration through the pores causing a very short cycle life, therefore, Celgard is not used for any commercially available silver zinc batteries.
The silver zinc battery separator is an insulator which must be resistant to degradation in strong alkali (such as potassium hydroxide) and heat. Further, the separator must be highly porous to allow migration of electrolyte and to provide a battery of high energy density. Another criterion is that the separator must exhibit low electrical resistance. A still further criterion is that a separator must inhibit migration of metal particles in electrolyte solution. In addition, the separator must be capable of inhibiting formation and growth of dendrites which can bridge the thickness of the separator after a period of time and cause shorting between electrodes of different polarity.
One of the other problems associated with silver zinc secondary batteries is capacity loss after each cycling which is due to a phenomena called zinc shape change. During each charge and discharge zinc oxide dissolves in electrolyte and re-plates back on the electrode. However, the zinc oxide does not re-plate necessarily at the same location. Zinc oxide usually dissolves from the top of the negative electrode and re-plates on the bottom, reducing the surface of active material. This phenomena will manifest itself by a gradual capacity loss.
Various prior art has attempted to remedy these problems. U.S. Pat. No. 5,336,573 discloses a method of making battery separators with high tensile strength by utilizing prior art technology for producing microporous membranes (extruding a mixture comprised of polymer, particulate filler and processing plasticizer to form a sheet, then calendar the sheet and extract the plasticizer in another step). instead of using a sheet die, they used a cross-head die and encapsulated a non-woven substrate inside two layers of microporous sheets. In a cross-head die, the processing mixture makes a 90 degree turn and splits to provide two feeds (one upper and one lower). At the same time, the fibrous sheet (non-woven) is fed into the die through a separate mandrel and is positioned between two feeds within the die. The two extruded feeds and the fibrous sheet meet close to the die""s exit. In this region the mixture from the feeds recombines while encapsulating the fibrous sheet within its core. The main objective of U.S. Pat. No. 5,336,573 is to produce a microporous sheet with a very high tensile strength.
The separator produced, using the method of this patent had large pores, due to the use of the non-woven, macroporous web encapsulated with a microporous membrane, since the pore diameter is a function of the fiber diameter which is usually in the range of 5 microns. Therefore, the separator described here cannot be used to minimize silver migration.
In U.S. Pat. No. 4,371,596 Sheibley describes producing a flexible porous battery separator for an alkaline cell by coating a woven or non-woven substrate with a slurry comprised of a copolymer or rubber-based resin (a binder), a polar organic plasticizer (must react with the alkaline electrolyte), an organic solvent and two or more inorganic or organic fillers with distinct particle sizes As the coating dries, each particle is coated with a thickness of plasticizer with the smaller particles filling the voids between the larger particles. The polar plasticizer preferentially deposits on and coats the surface of the polar filler materials within the substrate matrix"" thus, uniform pores are obtained when the plasticizer reacts with electrolyte. The pore size depends upon the thickness or width of the pathway, which in turns depends upon surface area of the fillers and the amount of the plasticizer.
Shiebly uses a blend of filler to make a coating solution to fill the large pores of the non-woven material. This product is not extruded, unlike the present invention. In the present invention, the filler is used to generate fine interconnecting pores. In the present invention, the polymer is used as a binder to attach the filler particles.
The prior art described by Sheibly disclose neither information regarding the average pore diameter of the resulting separator, nor information regarding the degree of improvement of the extended Agxe2x80x94Zn battery life. The pore diameter of the above invention not only depends on surface area of the filler as described but the average pore diameter also depends on fiber diameter of the woven and non-woven substrates used in the invention.
The main objective of the U.S. Pat. No. 4,371,596 is to reduce the very large pore size of a non-woven substrate and create a microporous membrane by a coating method. The pore diameters created by this method have not been disclosed and cannot be evaluated for colloidal silver migration in a silver zinc cell.
The U.S. Pat. No. 4,287,276 by Lundquist discloses a method for reducing the electrical resistant and improving dendrite resistance for alkaline battery separator by using high surface area filler. By using high surface area filler, the percent porosity of the separator is increased which results in a separator with high ion conductivity and low electrical resistance. In order to improve dendrite resistance of the alkaline battery separator.
The Lundquist patent, using high surface area filler, does not significantly reduce the pore diameter of the separator to minimize colloidal silver migration. Using high surface area filler, as described in Lundquist, does not significantly improve the cycle life of a silver zinc cell.
In order to significantly minimize colloidal silver migration, the pore diameter of the sheet has to be reduced to less than 0.005 microns.
The reduction of pore diameter to less than 0.005 cannot be achieved by using a blend of high-surface-area filler alone. It can not even be achieved by using a blend of fillers in which one of the fillers has an average pore diameter in the range of; 0.03 microns as used in the present invention. In order to produce a sheet of smaller than 0.005 micron pores, the sheet has to be further processed by the boiling step, as described in the current invention.
Lundquist added carbon black to the separator formed from polyolefin, a plasticizer and a filler with very large surface area of from 100 to 385 m2/ee and a pore volume of at least 0.0.075 cc/gm.
The average pore diameter created described in U.S. Pat. No. 4,287,278 is in the range of 0.05 to 0.10 microns and membranes produced by this method do not significantly delay the colloidal silver migration in a silver zinc cell.
U.S. Pat. No. 5,948,557 describes microporous material in the form of a thin sheet or tube having a thickness across the microporous material in the range of from 5 to 26 micrometers. The process for producing such microporous material is well known in prior art (briefly, extruding a mixture comprised of polymer particulate filler and a processing plasticizer to form a sheet), but, instead of using a sheet die and sending it through a calendar stack they have used a blown film die and its down stream.
The main objective of U.S. Pat. No.5,948,557 is to produce an extremely thin microporous membrane.
The current invention discloses a method of making microporous membranes with the average pore diameter in the range of 0.004 microns. This is the pore diameter that significantly delays the colloidal silver migration (delaying a short circuit in a silver zinc cell and extending the cell life). The smallest pore diameter that can be produced by the methods mentioned in the above prior art patents is at least one order of magnitude larger than the current invention.
In the current invention two criteria are used to reduce the average pore diameter. The first criteria is related to the particle size of two fillers and their ratio of the mix. The second and the most important criteria uses a phenomenon that creates a physical shrinkage of the matrix forming extremely small pore diameters. In this method, after the sheet is extruded and all of the plasticizer is extracted, the web is coated with a wetting agent and then dried. In the next step, the web is submerged in a tank of boiling water for one minute and then dried with air at room temperature overnight. The membrane shrunk between 10-20% in MD (machine direction) and the resultant membrane has an average pore diameter of 0.004 microns. The average pore diameter prior to the boiling step was measured and was 0.07 microns. The result indicates that the hydrophilic wetting agent which coats the membrane to will cause the shrinkage of the membrane matrix when water and heat are present. This shrinkage will result in significant reduction in membrane""s average pore diameter which is required to minimize colloidal silver migration. This result shows that producing pore diameter smaller than 0.01 micron can not be achieved by just using fillers with high surface area and additional shrinkage of the membrane is required to obtain pore size smaller than 0.01 micron. The shrinkage of the membranes does not occur when the wet-coated membrane is annealed, or exposed to hot air. Boiling water has to be present to shrink the membrane.
The present invention combats zinc shape change by its ability to be enveloped tightly around the electrodes. Because of the separator""s ability to be sealed tightly around the electrode the zinc oxide is not able to travel freely around the electrode and deposit in a different place than it was initially dissolved.
The present invention also provides a method for producing a battery separator which provides the micro-porosity of Cellophane, but which does not degrade in the alkaline electrolyte, as does Cellophane. The present invention is directed to a battery separator that has incorporated a blend of two TiO2 fillers where the particle size of the one filler is ten times smaller than the other filler to produce a membrane with pores small enough to minimize colloidal silver migration in a silver zinc cell or in a silver battery system.
This invention makes it possible to substantially improve cycle life, calendar life and performance of silver zinc batteries. It also reduces the assembly costs. In addition, the separator of the current invention reduces the assembly cost and opens new market opportunities for the silver battery systems. The sealability and envelopability of this separator make it suitable for manufacture by high speed enveloping machines. Therefore, if used as a separator, it will significantly reduce the silver zinc and other alkaline battery manufacturing costs
A general object of the current invention is to provide a battery separator for silver-zinc batteries with improved cycle life, calendar life, and performance.
A specific object of the current invention is to provide such a separator in the form of a microporous membrane with a controlled pore diameter.
A further specific object of this invention is to provide a microporous battery separator stable in KOH with a narrow range of pore size distribution and with an average pore diameter in a range of 0.1 to 0.01 microns.
A still further specific object of this invention is to provide a battery separator stable in KOH which significantly delays colloidal silver migration in batteries with positive silver electrodes.
A yet further specific object of this invention is to introduce a method for enveloping silver zinc battery electrodes in a sealable separator.
A final specific object of this invention is to produce a gas permeable microporous membrane for micro filtration and size exclusion.
According to one aspect of the invention, a method of creating a micro-porous membrane battery separator for silver zinc batteries includes combining two fillers with the same chemical formula but different particle size, blending a polyolefine polymer and a plasticizer, adding the blended polymer and plasticizer to the fillers to form a compound, and extruding the compound to form a thin sheet. The plasticizer is then extracted, and the process finishes with the coating of the extracted sheet with a wetting agent, then drying the coated sheet, and, finally, the immersing the coated sheet at least for 1 minute in boiling water, followed by air drying.
According to a second aspect of the invention, the wetting agent is selected from the group consisting of Dodecylphenoxy polyethoxy ethanol, and looctyl phenyl polyethoxy ethanol.
According to a third aspect of the invention the thickness of the sheet is between 3 and 10 mils.
According to a fourth aspect of the invention the fillers further comprise titanium dioxide.
According to a fifth aspect of the invention the polyolefine has a molecular weight of at least 3,000,000.
According to yet another aspect of the invention the polyolefine is a blend of between 90 and 95 percent by weight of ultra high molecular weight polyethylene, and between 5 and 10 percent by weight of high density polyethylene.
According to still another aspect of the invention the polyolefine is a blend of between 10 and 30 percent by weight of polypropylene, and between 70 and 90 percent by weight of ultra high molecular weight polyethylene.
According to yet one more aspect of the invention one of the fillers is a pigment grade titanium dioxide Rutile of 0.18 micron particle diameter and the other filler is an ultra fine UV grade titanium dioxide Rutile filler of 0.017 micron particle diameter.
According to still another aspect of the invention the plasticizer is selected from the group consisting of petroleum oils, lubricating oil, fuel oil, tall oil, and linseed oils.
According to a final aspect of the invention a wetting agent is used for coating after extraction of plasticizer.